CN101532088B - Method for recovering zinc and manganese from waste dry batteries and directly preparing industrial desulfurizer - Google Patents
Method for recovering zinc and manganese from waste dry batteries and directly preparing industrial desulfurizer Download PDFInfo
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- CN101532088B CN101532088B CN2009100258188A CN200910025818A CN101532088B CN 101532088 B CN101532088 B CN 101532088B CN 2009100258188 A CN2009100258188 A CN 2009100258188A CN 200910025818 A CN200910025818 A CN 200910025818A CN 101532088 B CN101532088 B CN 101532088B
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000011701 zinc Substances 0.000 title claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 20
- 239000002699 waste material Substances 0.000 title claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 11
- 239000011572 manganese Substances 0.000 title claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 26
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 11
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- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims abstract description 10
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 10
- LNRYQGINUXUWLV-UHFFFAOYSA-N [Mn].[Fe].[Zn] Chemical class [Mn].[Fe].[Zn] LNRYQGINUXUWLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 6
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- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
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- 238000004090 dissolution Methods 0.000 claims description 2
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- 239000011593 sulfur Substances 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 13
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- 238000011068 loading method Methods 0.000 description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 235000013980 iron oxide Nutrition 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
A process for recovering Zn and Mn from used dry batteries and directly preparing desulfurizing agent for industrial purpose includes such steps as breaking the used dry batteries, dissolving Mn, zn and Fe in dilute sulfuric acid, filtering to remove insoluble substance, neutralizing the filtrate with sodium carbonate solution to generate deposit, baking, adding hydroxymethyl cellulose, cement 425 and attapulgite, mixing, adding water, kneading, extruding to obtain strips, drying at 95-110 deg.C, and baking at 300 deg.C. Compared with similar products at home and abroad, the performance indexes of the iron-manganese-zinc series desulfurizer produced by using the reclaimed material of the waste zinc-manganese battery as the raw material have the characteristics of high component content, high penetrating sulfur capacity, moderate side pressure strength and low abrasion, all technical indexes of the desulfurizer all reach the technical indexes of the similar products at home and abroad, and the main indexes of the desulfurizer are better than those of the similar products at home and abroad, so that the desulfurizer can meet the requirements of industrial use and can be popularized and used as a novel industrial practical purifying agent.
Description
Technical Field
The invention relates to resource recycling of a zinc-manganese dry battery, in particular to a method for preparing an industrial desulfurizer by using zinc-manganese-iron recovered from a waste zinc-manganese battery.
Background
The zinc and manganese dry battery is a disposable power supply, the cathode is zinc, and the anode carbon bag mainly comprises the following components: carbon rod, manganese dioxide, carbon powder, acetylene black, ammonium chloride, zinc chloride, electric paste, iron shell and the like. The recycling of waste batteries is a worldwide problem, and no generally accepted economic and effective comprehensive utilization process is used for recycling the waste zinc-manganese batteries so far. The battery is a necessity closely related to ordinary people, plays a great role in the life of people, and has a great number of products taking the battery as an energy source, but the wide use of the battery drives the development of the battery industry and also causes the consumption of resources; on the other hand, because the use of the battery is basically disposable, the recovery rate is very low, the waste battery causes serious environmental pollution, china is the first major world in which the zinc-manganese battery is sold, the yield is only 50 hundred million in 1988, 100 hundred million in 1994, 150 hundred million in 2003, 190 hundred million in 2006, accounts for half of the world yield, and the domestic sales volume is 110-120 million. Every year, calculated by 100 hundred million batteries, resources such as 15.6 million tons of zinc, 22.6 million tons of manganese dioxide, 2.8 tons of copper, 2.7 million tons of zinc chloride, 7.9 million tons of ammonium chloride, 4.3 million tons of carbon rods and the like are consumed all year round, and no ideal solution exists for the treatment problem of the waste zinc-manganese batteries at present internationally, while the existing recovery treatment technologies mainly fall into three categories: dry, wet and dry-wet processes.
The dry method, also called as fume method or fire method, utilizes the difference of melting point, boiling point and vapor pressure of various metals or metal compounds to separate and extract at different temperatures, thereby achieving the purpose of resource recovery. The method has large one-time investment and high energy consumption.
The wet method is to leach the waste batteries with acid to produce soluble salt, and then to extract metals such as zinc, manganese, etc. by electrolysis. The method needs to be separated for several times in the process and is difficult to process.
The dry-wet method combines the advantages of the dry method and the wet method, has good effect, but has complex working procedures and high cost.
At present, various recovery methods reported at home and abroad are as follows: the research on the preparation of manganese-zinc ferrite by co-precipitation of waste alkaline batteries by Matilia et al (see: the artificial crystal article, volume 35, phase 2, 2006, 4), the research on the preparation of zinc-manganese composite micro-fertilizer by waste batteries by Peiying et al (see: phase 1P 53 in the chemical world), the research on the recovery and utilization of waste zinc-manganese batteries by Cheng Jianliang et al (see: the manganese ferrite prepared by waste batteries, volume 22, phase 1, 2004, 2 in the China manganese industry), the research on the recovery and utilization of waste zinc-manganese batteries by Zhao Dongjiang et al (see: the waste zinc-manganese batteries, volume 34, phase 10, 2005, 10) and the like, which are not really suitable for industrialization due to high cost, impracticability in economy or technical defects and the like. The development trend of the waste zinc-manganese battery recycling technology is to reduce the cost, fully utilize resources in the waste zinc-manganese battery, avoid difficult chemical separation processes and finally prepare products with higher added values.
Disclosure of Invention
The invention uses the recovered material of waste battery as base material, and is characterized by that it utilizes the self-attribute of battery, couples unique chemical reaction, only needs one-step leaching and 100% regeneration of metal resource to obtain unique mixture product, at the same time develops a conversion absorption type zinc-manganese-iron series desulfurizing agent (temporarily defined as QS type desulfurizing agent) which can be extensively used in the purification process of raw material gas of large, medium and small ammonia synthesis equipment, methanol synthesis equipment and organic synthesis equipment, and the sulfur content of various raw material gases (oil) treated by QS type desulfurizing agent can be reduced to below 0.1 ppm. The invention simplifies the processing process and finally achieves the purposes of reducing pollution and recycling. The uniqueness is that the recycling technology and cost are integrated with the development of application products, and the operability is very strong.
The technical scheme of the invention is as follows:
a method for recovering zinc and manganese by using waste dry batteries and directly preparing an industrial desulfurizer comprises the following steps:
1. recovery of metals
Step 1, acid dissolution: using dilute sulphuric acid with the concentration of 2-6M to crush the zinc-manganese dry battery, heating the zinc-manganese dry battery to 70-90 ℃ after the solid-liquid ratio is 1: 4-1: 8 (V/V) for 2-6 hours, stirring and reacting for 3-6 hours to ensure that the acid leaching reaction is completely carried out, and stopping heating and stirring.
Step 2, filtering: filtering to remove the insoluble substances, and filtering to remove the insoluble substances,
step 3, neutralization: neutralizing the filtrate with 10-30 wt% concentration sodium carbonate solution, 2-3mol/L sodium hydroxide solution or 2-3mol/L ammonium bicarbonate solution to produce precipitate,
step 4, roasting: filtering out the precipitate, baking the precipitate at 150-450 ℃ after drying to obtain a mixture of metal oxides,
2. preparation of desulfurizing agent
Step 5, batching: weighing the following components in percentage by mass, taking the materials, and putting the materials into a mixing tank for proportioning and mixing to ensure that the materials are as uniform as possible:
78-97% of the mixture of metal oxides prepared in step 4,
1.0 to 20 percent of hydroxymethyl cellulose,
425% of cement by weight, 0-15%,
0 to 15 percent of attapulgite,
and 6, kneading: adding a proper amount of water to knead the mixture,
step 7, extruding and forming: the strip is extruded on a strip extruding machine,
and 8, drying: drying the formed strips at 95-110 deg.C for 18-20 hr to reduce the water content from about 40% to 5%,
step 9, roasting: heating at a rate of about 50 deg.C/hr to 300 deg.C for 1.5 hr, and cooling to room temperature to obtain the industrial desulfurizer.
In the preparation method of the industrial desulfurizer, the neutralization in the step 3 can be carried out at 70-80 ℃, and the solution after neutralization is kept stand for a period of time to ensure that the neutralization reaction is thorough.
In the preparation method of the industrial desulfurizer, a rolling step can be added between the step 5 and the step 6: dry-grind on a roller mill for 20 minutes to ensure that the lumps of material are eliminated and mixed thoroughly.
The basic principle of the invention is as follows: the waste zinc-manganese battery is leached by sulfuric acid, and the metal zinc, iron and copper are reacted with sulfuric acid to generate corresponding sulfate aqueous solution. The manganese dioxide material and iron sheet in the waste battery are leached out in the sulfuric acid solution at the same time, and the leaching is strengthened by utilizing the oxidation-reduction action of the manganese dioxide and ferrous iron, so that the leaching rate of the manganese dioxide and zinc is improved, the zinc, manganese and iron in the waste battery are comprehensively recovered, the roasting process of the conventional method is omitted, the secondary pollution and energy consumption caused by the secondary pollution and energy consumption are eliminated, the metal recovery rate is improved, and the cost is reduced. The recovered metal oxide mixture is processed into a large amount of manganese-zinc-iron desulfurizing agent required in the current market through a proper process technology, so that the market application and the economical efficiency of the recovered and developed products of the dry battery become possible.
The method for recovering zinc and manganese by using waste dry batteries and directly preparing the industrial desulfurizer has reasonable technical process route, is economical and feasible, well solves the problems of recovery cost and application market of products, and can realize the recovery and utilization of zinc-manganese series waste batteries in a real sense.
Drawings
FIG. 1 is a schematic diagram of a desulfurizing agent penetration sulfur capacity detection process, wherein 1, a dehydration tank; 2. a devulcanizer; 3. a rotameter; 4. na (Na) 2 S solution storage bottles; 5. a metering tube; 6. h 2 An S generator; 7. a saturator; 8. a reactor; 9. a gas-liquid separator; 10. h 2 S, absorbing the bottle; 11. h 2 An S absorption tube; 12. inlet gas sampling point.
Detailed Description
EXAMPLE 1 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 3.4M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 6, after soaking for 6 hours, starting heating, controlling the temperature at 70-75 ℃ to react for 6 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using a sodium carbonate solution with the concentration of 10 percent (Wt), controlling the temperature to be 70 ℃ for 1 hour in order to ensure the neutralization reaction to be complete, standing the neutralized liquid for a period of time, filtering to separate solid from liquid, drying the solid, and roasting at 450 ℃ to obtain 502 g of a mixture of the needed manganese, zinc and iron metal oxides.
EXAMPLE 2 preparation of a mixture of Metal oxides
The method comprises the steps of cleaning zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 3.86M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 6, after soaking for 4 hours, starting to heat, controlling the temperature to be 80-85 ℃ to react for 4.5 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using a sodium carbonate solution with the concentration of 20% (Wt), controlling the temperature to be 75 ℃ for 1 hour in order to ensure the neutralization reaction to be complete, standing the neutralized liquid for a period of time, filtering to separate solid from liquid, drying the solid, and roasting at 450 ℃ to obtain 538 g of a mixture of the needed manganese, zinc and iron metal oxides.
EXAMPLE 3 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, drying in the air, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 5.15M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 6, soaking for 2 hours, starting heating, controlling the temperature to be 85-90 ℃ to react for 3 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using a sodium carbonate solution with the concentration of 30% (Wt), controlling the temperature at 80 ℃ for 1 hour to ensure that the neutralization reaction is complete, standing the neutralized liquid for a period of time, filtering to separate solid from liquid, drying the solid, and roasting at 450 ℃ to obtain 554 g of a mixture of manganese, zinc and iron metal oxides.
EXAMPLE 4 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries with different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 6M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 4, after soaking for 2 hours, starting to heat, controlling the temperature to be 80-85 ℃ to react for 3 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using an ammonium bicarbonate solution with the concentration of 3mol/L, controlling the temperature at 80 ℃ for 1 hour to ensure that the neutralization reaction is complete, standing the neutralized liquid for a period of time, filtering to separate solid from liquid, drying the solid, and roasting at 450 ℃ to obtain 541 g of a required mixture of manganese, zinc and iron oxides.
EXAMPLE 5 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 2M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 8, after soaking for 5 hours, starting heating, controlling the temperature to be 85-90 ℃ to react for 6 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using a sodium hydroxide solution with the concentration of 3mol/L, controlling the temperature at 80 ℃ for 1 hour to ensure that the neutralization reaction is complete, standing the neutralized liquid for a period of time, filtering to separate solid from liquid, drying the solid, and roasting at 450 ℃ to obtain 489 g of a required mixture of manganese, zinc and iron oxides.
EXAMPLE 6 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 3.86M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 6, starting to heat after soaking for 4 hours, controlling the temperature to be 80-85 ℃ to react for 4.5 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using a sodium hydroxide solution with the concentration of 2mol/L, controlling the temperature to be 75-80 ℃ for 2 hours in order to ensure that the neutralization reaction is complete, filtering to separate solid from liquid after the neutralization solution is kept stand for a period of time, and drying and roasting the solid at 150 ℃ to obtain 542 g of a mixture of manganese, zinc and iron metal oxides.
EXAMPLE 7 preparation of a mixture of Metal oxides
Washing zinc-manganese waste batteries of different specifications and types collected from environmental sanitation departments with water, airing, manually cutting and crushing, soaking in dilute sulfuric acid with the concentration of 3.86M, wherein the volume ratio of the waste batteries to the dilute sulfuric acid is 1: 6, starting to heat after soaking for 4 hours, controlling the temperature to be 80-85 ℃ to react for 4.5 hours, completely carrying out acid leaching reaction, and stopping stirring and heating. Filtering to remove dregs, neutralizing and precipitating the liquid by using an ammonium bicarbonate solution with the concentration of 2mol/L, controlling the temperature to be 75 ℃ for 3 hours in order to ensure that the neutralization reaction is complete, filtering to separate solid from liquid after the neutralization solution is kept stand for a period of time, and drying and roasting the solid at 450 ℃ to obtain 482 g of a mixture of manganese, zinc and iron metal oxides.
Example 8 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 2 g of hydroxymethyl cellulose, 0g of 425 cement and 3 g of attapulgite, putting the mixture into a mixing tank for mixing and proportioning to be as uniform as possible, then carrying out rolling, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure strip extruder, putting the extruded and formed strip into a tray, putting the tray into an oven, drying for 20 hours at 95 ℃, reducing the water content to 5%, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
Example 9 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 1 g of hydroxymethyl cellulose, 3 g of 425 cement and 4 g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then rolling, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying for 20 hours at 110 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
EXAMPLE 10 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 3 g of hydroxymethyl cellulose, 3 g of 425 cement and 2 g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then rolling, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying for 20 hours at 100 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
Example 11 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 25 g of hydroxymethyl cellulose, 2 g of 425 cement and 1 g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then rolling the mixture, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying the tray for 20 hours at 110 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
EXAMPLE 12 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 5 g of hydroxymethyl cellulose, 19 g of 425 cement and 4 g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then rolling the mixture, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying the tray for 20 hours at 110 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
Example 13 preparation of Industrial desulfurizing agent
Taking 100g of the mixture of the metal oxides, adding 6 g of hydroxymethyl cellulose, 3 g of 425 cement and 19 g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then carrying out rolling, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying for 20 hours at 110 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
Example 14 preparation of desulfurizing agent for Industrial use
Taking 100g of the mixture of the metal oxides, adding 2 g of hydroxymethyl cellulose, 1 g of 425 cement and 0g of attapulgite, putting the mixture into a mixing tank for mixing ingredients so as to be as uniform as possible, then rolling the mixture, carrying out dry grinding for 20 minutes, adding a proper amount of water for blending, adding water and then grinding for 20 minutes so as to enable the mixture to be kneaded and formed, extruding the mixture on an oil pressure extruding machine, loading the extruded strip into a tray, putting the tray into an oven, drying the tray for 20 hours at 110 ℃, reducing the water content to below 5 percent, then roasting, raising the roasting temperature at the speed of about 50 ℃ for hours, raising the temperature to 300 ℃, keeping the temperature at 300 ℃ for 1.5 hours, and cooling to obtain the industrial desulfurizer.
Example 15 measurement of desulfurization Performance of desulfurizing agent obtained by the method of the present invention
1. Penetration of sulfur capacity:
the technical index of the penetration sulfur capacity is the most important index for representing the desulfurization performance of the desulfurizer.
The process flow of the measuring apparatus is shown in FIG. 1
Measurement conditions (see Table 1)
TABLE 1 Activity test conditions of desulfurizing agent Zn-Mn-Fe
| Index name | Index value |
| Inner diameter mm of the reactor | Phi 10 hard glass tube |
| Desulfurizing agent loading capacity ml | 2.0 |
| Desulfurizing agent granularity mm | 0.425～0.850 |
| Reaction temperature C | 220 |
| Space velocity h -1 | 3000±20 |
| Index name | Index value |
| System pressure MPa | Atmospheric pressure |
| The content of hydrogen sulfide in the feed gas is g/Nm 3 | 1.0～4.0 |
* The raw material gas is a mixed gas of nitrogen and hydrogen (V/V; 3: 1)
Measurement method
Smashing a desulfurizing agent sample, sieving the smashed desulfurizing agent sample by using a test sieve with the aperture of 0.85-1.18 mm, drying the smashed desulfurizing agent sample for 1 hour at 120 ℃, tightly packing 10ml of sample by using a 10ml measuring cylinder, weighing the sample to obtain the bulk density, and weighing the sample with the mass equivalent to 2 ml.
Reactor filling
Slowly loading the sample into a clean reactor, lightly knocking the wall of the reactor while loading to ensure that the catalyst is tightly filled, and connecting the system.
Displacement system
And after the system is connected, leakage test is carried out, and then nitrogen and hydrogen are opened for replacement.
To the system H 2 S, sampling and analyzing the content of the hydrogen sulfide in the inlet gas, and adjusting Na according to the analysis result 2 S amount, making H in semi-water gas 2 The S content is 3.0-5.0 g/Nm 3 Range, H 2 The S analysis was performed using the mercury method, as specified in HG/T2513, appendix B.
General formula H 2 And after 24h of S gas, putting wet test paper soaked by 100g/L lead acetate solution at the outlet end of the reactor, and replacing the test paper every 4 h. When the test paper becomes black, the airspeed and the inlet hydrogen sulfide concentration are re-calibrated. After the conditions are stable, if the test paper is still black, the test paper is considered to be penetrated, the ventilation is stopped, the system is closed, all the cuk in the reactor is discharged, a small amount of quartz sand mixed in the desulfurizer is carefully removed, the quartz sand is ground into powder, the powder is dried for 1 hour at 120 ℃, and the once-through sulfur capacity of the desulfurizer is measured by a combustion neutralization method. The computational analysis method is as specified by HG/T2513.
2. Determination of the radial crush Strength of the test specimens
The specific determination method is as follows:
a. 10 samples were taken at random.
b. The side pressure strength was measured using a QCY-602 electric strength tester load cell.
c. The maximum and minimum values of the lateral pressure intensity in 10 particles are rejected.
d. The length of each pellet was measured.
e. The measured average radial crush strength was calculated by the following formula
10 10
P＝∑Pi/∑li(N/cm)
i＝1 i＝1
3. Determination of abrasion
The abrasion loss of the sample was measured with a CM2 type abrasion meter.
The measurement conditions were as follows: see the specification HG/T2976, in which the sample is dried at (120. + -. 5) ℃ for 2h.
And (3) test results:
the samples prepared by the above-mentioned desulfurizing agent preparation method were satisfactory in the results of the measurement of the comprehensive properties, and the average penetration sulfur capacity was 23.7% (the measurement conditions are shown in Table 1), the side pressure strength was 63.2N/cm, and the abrasion was 8.5%
TABLE 2 determination of breakthrough sulfur capacity
| Test specimen | 1* | 2* | 3* |
| Penetration sulfur capacity | 21.1 | 24.3 | 25.7 |
Testing of operating conditions:
the relationship between temperature and breakthrough sulfur capacity is shown in Table 3
TABLE 3 relationship of temperature to breakthrough sulfur capacity
| Temperature of | 40 | 300 | 350 |
| Penetration sulfur capacity | 7.2 | 26.7 | 34.2 |
The relationship between space velocity and breakthrough sulfur capacity is shown in Table 4
TABLE 4 relationship of space velocity to breakthrough sulfur capacity
| Space velocity h -1 | 1000 | 1500 | 3000 |
| Penetration sulfur capacity | 33.3 | 30.1 | 26.7 |
The test results show that the selected formula product reaches the quality level of the commercial product and can be used under a wider range of industrial operation conditions,
and (4) conclusion:
compared with similar products at home and abroad, the performance index of the zinc-manganese-iron series desulfurizer produced by using the reclaimed material of the waste zinc-manganese battery as the raw material has the characteristics of high component content, high penetrating sulfur capacity, moderate side pressure strength and low abrasion, all technical indexes of the zinc-manganese-iron series desulfurizer reach the technical indexes of the similar products at home and abroad, and the main index of the zinc-manganese-iron series desulfurizer is better than that of the similar products at home and abroad, so that the zinc-manganese-iron series desulfurizer can meet the requirement of industrial use and can be popularized and used as a novel industrial practical purifying agent.
Claims (3)
1. A method for recovering zinc and manganese from waste dry batteries and directly preparing industrial zinc-manganese-iron desulfurizer is characterized by comprising the following steps:
1. recovery of metals
Step 1, acid dissolution: the crushed zinc-manganese dry battery is treated with dilute sulfuric acid with the concentration of 2-6M according to the solid-liquid volume ratio: leaching at a ratio of 1: 4-1: 8 for 2-6 hr, heating to 70-90 deg.C, stirring for 3-6 hr to complete the acid leaching reaction, stopping heating and stirring,
step 2, filtering: filtering to remove the insoluble substances, and filtering to remove the insoluble substances,
and step 3, neutralizing: neutralizing the filtrate with 10-30 wt% concentration sodium carbonate solution, 2-3mol/L sodium hydroxide solution, or 2-3mol/L ammonium bicarbonate solution to produce precipitate,
and step 4, roasting: filtering out the precipitate, drying the precipitate, roasting at 350-450 deg.C to obtain a mixture of metal oxides,
2. preparation of desulfurizing agent
Step 5, batching: weighing the following materials according to the mass percentage of the formula, putting the materials into a mixing tank for proportioning and mixing so as to ensure that the materials are as uniform as possible:
78-97% of the mixture of metal oxides prepared in step 4,
1.0 to 20 percent of hydroxymethyl cellulose,
425% of cement by weight, 0-15%,
0 to 15 percent of attapulgite,
step 6, kneading: adding a proper amount of water to knead the mixture,
step 7, extruding and forming: the strip is extruded on a strip extruding machine,
and 8, drying: drying the formed strips at 95-110 ℃,
step 9, roasting: roasting at 300 deg.c for 1.5 hr, and cooling to room temperature to obtain the industrial desulfurizing agent.
2. The method for preparing an industrial desulfurization agent according to claim 1, wherein: the neutralization described in step 3 is carried out at 70-80 ℃.
3. The method for preparing an industrial desulfurization agent according to claim 1, wherein: between the step 5 and the step 6, a rolling step is added: dry-milling on a roller mill for 20 minutes.
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| CN102134521B (en) * | 2010-01-21 | 2013-10-16 | 泰山学院 | Method for producing sulfur-fixing agent and sulfur-fixing briquette by using waste dry battery |
| CN103545538A (en) * | 2013-11-06 | 2014-01-29 | 安徽工业大学 | Method for preparing raw material for manganese series ferroalloy by using waste zinc-manganese dry battery |
| CN106450370A (en) * | 2016-11-24 | 2017-02-22 | 张灿 | Dry battery recycling method |
| CN107804876A (en) * | 2017-12-05 | 2018-03-16 | 王龙 | Manganese dioxide and ammonium chloride extraction element in a kind of waste battery |
| CN111089935B (en) * | 2018-10-24 | 2023-01-03 | 中国石油化工股份有限公司 | On-site natural gas dry desulfurizing agent sulfur capacity testing method |
| CN111106359B (en) * | 2020-01-17 | 2020-10-16 | 三门踱哒环保设备有限公司 | Automatic metal collecting device in waste battery |
| CN111468135B (en) * | 2020-04-28 | 2022-07-12 | 武汉科林化工集团有限公司 | Preparation method of novel purifying agent for removing carbonyl metal |
| CN115350588B (en) * | 2022-08-16 | 2024-04-12 | 沈阳三聚凯特催化剂有限公司 | Method for recycling deactivated iron-based desulfurizing agent |
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